Derivatives of behenic acid amide



Patented May 1, 1951 DERIVATIVES OF BEHENIC ACID AMIDE Josef Pikl, Glassboro, N. J., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Original application June 3, 1942,

Serial No. 445,675. Divided and this application June 26, 1947, Serial No. 757,336

2 Claims. (Cl. 260-4045) This application is a division of my copending application Serial No. 445,675, filed June 3, 1942, (which matured into Patent No.'.2', 426,790). The invention herein relates to the production of novel derivatives of behenic acid amide and other higher fatty acid amides.

It is an object of this invention to produce novel derivatives of behenic acid amide or other higher fatty acid amides possessing valuable properties as agents for producing water-repellent efiects upon textile fiber or which may serve as useful intermediates for the production of such agents. Other and further important objects of this invention will appear as the description proceeds.

In my parent application above identified, I have described and claimed a process for converting behenic acid amide into a reaction prod uct possessing CHzCl groups attached to nitrogen atoms. I have further shown there that the Cl atoms in such compounds are readily exchanged for thiocyano radicals, forming thiccyano intermediates which may be further converted into corresponding quaternary-ammonium thiocyanates. My present application is concerned primarily with these thiocyano compounds, both intermediates and quaternary compounds.

The complete prccess according to my invention comprises as a first step the reaction of behenic acid amide with formaldehyde-yielding agents and hydrogen chloride under conditions which will avoid the formation of substantial quantities of methylene-dibehenamide. I achieve this object by modifying the steps of procedure in such a manner as to avoid any high concen trations of behenic acid amide in the presence of the formaldehyde-yielding agent. Two procedures are possible for this purpose. Assuming that the reaction is carried out in a liquid medium such as benzene as in the other processes of the art, I may suspend the requisite quantity of parafprmaldehyde or trioxymethylene in the benzene and then pass into it gradually from different sources of supply hydrogen chloride on the one hand and behenic acid amide on the other hand. Alternatively, I may pass all three reagents from different sources of supply into a vessel containing benzene. Or again, the formaldehyde and the behenic acid amide may be mixed together dry and passed gradually into a vessel containing benzene while simultaneously passing hydrogen chloride from another sour e into the vessel' It will be noted that the lastmentioned case, although the paraforrnaldehyde is in constant contact with the behenic acid amide, the fact that the mixture is dry and is out of contact with hydrogen chloride prevents the formation of the undesirable bis-compound.

By proceeding in the above manner I have succeeded in obtaining compounds which according to their analyses contain between one and two behenamido chains per CHzCl group. Without limiting my invention to any particular theory, I venture the hypothesis that the product probably consists principally of a bis-chloromethylene dimethylene tribehenamido com pound as represented by the following formula:

wherein R designates the radical Call-I43.

Other possible components of the mixture are the corresponding methylene-bis-amido compounds and a trimethylene-tetrakisamido compound of the probable formula:

In all probability, all of these components are present in the products of my invention, the exact pro-portions of these in each case depending on the temperature, duration and other specific conditions of the reaction.

The above three different products are related in structure, and the more complex compounds may be brought together under the general formula:

wherein :1: stands for 1 or 2.

The above intermediate products are very reactive and may be reacted with potassium-thiccyanate or lead-thiocyanate according to my US. Patent No. 2,331,276, whereby to replace the chlorine atoms by thiocyano radicals, SON. These in turn may be reacted with pyridine or other tertiary amines to produce the corresponding quaternary-ammonium thiocyanates, analogous to the compounds described and claimed in my U. S. Patent No. 2,402,526.

On the other hand, if allowed to stand for some time without reacting with pyridine or other tertiary amines, the said thiocyanates undergo isomerization to give the corresponding isothiccyanates which may be applied to fabric from organic solution according to my said U. S. Patent No. 2,331,276, but again give water-repellency effects on fiber which are outstanding in their high initial power and fastness cualities.

If, in the above series of reactions, hydrogen bromide is employed in lieu of hydrogen chloride the corresponding methylene-bromide derivative may be obtained.

Without limiting .my invention the following ztion wa continued for another hour. vent was evaporated and'a hard, waxy massobitainedas a residue.

examples are given to illustrate .my preferred mode of operation. The parts mentionedare by weight.

EXAMPLE I Part A.Preparation of the chloromethylam de compound Eighty-five parts of behenic-acid'amide "(M.P. 114 C.) were dissolved in 500 parts of hot benzene and the solution then gradually added to a suspension of parts of paraformaldehyde in 200 parts of benzene heated to 80 C. while a stream of hydrogen chloride was passed into the reaction mixture. The reaction flask was connected through a water separator to a reflux condenser and provided with an agitator. In forty-five minutes the addition of the behenic-acid amide'solution was complete, giving a clear reaction mixture. Thesolution was heated for another half hour to insure complete reaction and then evaporated in vacuo on the steam bath. The resulting chloromethylamide was a low melting wax which decomposed with water.

Part B.--C'om2ersion into thz'ocyanate compounds Eighty-five parts of the chloromethylamide obtained according to Part A were dissolved in 500 parts of carbon tetrachloride and then reacted with 80 parts of lead thiocyanate'at 80 C. After the reaction was complete the solution was filtered from the inorganic salts, and the product,

a tan colored low melting wax, was recovered from the solvent by evaporation. It was readily soluble in benzene and in carbon tetrachloride, and gave with pyridine a water-soluble quaternary ammonium salt. It analyzed as follows:

Nitrogen: 5.85%; sulfur: 5.57%

The above analysis agrees closely with the empirical formula C72H13'7O'3N5S2, which would be required if the compound is a bis-(thiocyanomethylene)-dimethylene-tribehenamide as hypothesized in the general discussion above.

When this product was applied to cotton or wool from an organic solvent at a concentration of 5%, and the latter then subjected to baking, in standard manner, i. e., at a temperature between 105 and 150 C,., it gave a strongly waterrepellent fabric, the properties of which were not impaired by washing in a boiling soap solution or by extraction with a warm dry-cleaning solvent. When tested according to the standard method for testing water-repellency (Am. Dyest. Reporter, vol. 31, p. 8), this fabric was found to be remarkably superior as regards permanence (i. e., fastness to laundering and dry-cleaning), to a fabric similarly treated with the thiocyanate obtained in analogous manner from stearic-acid amide.

EXAMPLE II Part A.-Prepamtion of chloromethylamide compound One hundred thirteen parts of behenamide were dissolved in 500 parts of benzene and then added to a suspension of parts of paraformaldehyde in 200 parts of benzene While passing in a stream of hydrogen chloride at the boiling point of the reaction mixture. In one hour all the amide had been added, and the heating of the clear solu- Thesol- It contained 5.25% of chlorine. This is equivalent to about two fatty-acidzamideslfor each chlorineatom.

The:abovejproductreacted readily with triethylamine and pyridine to give Water-soluble products which foamed strongly in warm water and which gave excellent water repellency when applied to cotton or regenerated cellulose from aqueous solution, followed by drying and heating in standard manner.

Part.B.--C'0nversion into thiocyanate Sixty parts of the chloromethylamide obtained in Part A were dissolved in 500 parts of carbon tetrachloride andreacted at C. for one hour with 60 parts of lead thiocyanate. The inorganic salts were filtered ofi and a clear, light strawcolored solution was obtained. On evaporation of the solvent, the product analyzed .at 5.46% nitrogen and 4.33% sulfunwhich is about equivalent to two long-chain amido radicals for each sulfur atom.

This product gave excellent water repellency when applied, in standard manner, to cotton, wool or rayon.

Although'the above discussion and examples have been limited particularly to behenic acid amide,in view of the difiiculty of converting this amide into a ohloromethylene compound by'the older processes of the art, my invention is nevertheless of'ageneric nature and may be applied also to such amides which encounter no special difiiculties by the old processes. Thus they may be applied to stearamide, lauramide,'montanicacid amide, and in general to any amide of the formula RCONH2, wherein R is an alkyl or cyclo-alkyl radical of at least nine carbon atoms.

It will be understood that many other variations and modifications are possible inthe procedures above outlined without departing from the. spirit of this invention.

I claim as my invention:

1. A compound of the general'formula wherein R designates the radical 021E143, while Y designates a radical selected from the group consisting of thiocyanate and isothiocyanate. '2. A compound of the general formula (lam-q (fiHg-Y R-o O-N-l: CHz-N -CH2-N-C o-n wherein Y designates a radical selected from the group consisting of thiocyanate and isothiocyanate, While :c stands for a numeral of the group consisting of 1 and 2, said compound being characterized by its capacity to react with tertiary nitrogenous bases to produce a water-soluble quaternary compound.

J OSEF PIKL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,331,276 Pikl Oct..5, 1943 2,402,526 Pikl June 25,1946 2,426,790 Pikl Sept. 2, 1947 FOREIGN PATENTS Number Country Date 471,130 Great Britain Aug. 27, I939 

1. A COMPOUND OF THE GENERAL FORMULA 